JP2008132654A - Laminated sheet for thermoforming - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer type thermoforming laminate having a curable resin layer so that a peelable film is not peeled off during sheet molding or during thermoforming and can be quickly peeled off after thermoforming. To provide a sheet.
A thermoformed laminated sheet in which at least a peelable film layer, a curable resin layer, a decorative layer, and an adhesive layer showing adhesion to an adherend are laminated in this order, A laminated sheet for thermoforming, wherein an absolute value of a difference in wetting index after thermoforming of the peelable film layer and the curable resin layer is in a range of 0 to 12 dyn / cm.
[Selection figure] None

Description

  The present invention relates to a laminate sheet having a decorative layer, for example, a laminate sheet for molding useful as a sheet that does not require an outer layer coating used for automobile-related members, construction-related members, home appliances, and the like. It is related with the transfer-type laminated sheet for thermoforming which removes a peelable film after attaching a decorating layer to a to-be-decorated body with a heat | fever and a pressure.

In general, when a colored resin molded body is manufactured, there are a method of kneading a pigment into the resin itself, coloring it and molding it by injection molding or the like, and a method of spraying the molded body. For example, when a metallic design is required, a coating method is often used rather than a coloring method because of the difficulty of kneading metal pigments and the tendency of pigment flow to be noticeable. In the case of the coating method, the effect of surface protection can be expected by baking the coating film to crosslink the polymer component. In recent years, from the viewpoint of protecting the working environment against the discharge of volatile organic solvents and protecting the external environment, the use of water-based paints and powder paints instead of paints using volatile organic solvents has also been attempted. It has been. However, only a limited number of designs can be expressed by a solvent-free coating method.
On the other hand, the method of applying a complicated design such as printing on the surface of the molded body cannot be handled by the coloring method or the coating method.

  On the other hand, there is known a method in which a decorative sheet having a decorative layer is integrated with an adherend such as a molten resin or a resin molded body by thermoforming to perform decorative molding. According to this method, it is possible to produce a resin molded member having an arbitrary design without a solvent.

Conventionally, the decoration method at the time of thermoforming is a vacuum forming method in which the decorative sheet having a decorative layer is sufficiently thermoplasticized and then the sheet and the adherend are shaped in a vacuum state, or a concave mold and A press molding method (match mold molding method) in which the sheet and the adherend are sandwiched between convex molds, or after the sheet has been preliminarily molded by a press molding method or the like in advance. Further, there is an insert injection molding method in which a molten resin is injected and molded in a state where the sheet is mounted in a mold.
These decorating methods are known in which the decorative layer is not damaged such as scratches at the time of molding, so that a peelable film is provided on the decorative layer in advance and the peelable film is peeled off after molding, The decorative sheet used for the decoration method is called a transfer mold and has been studied.

  As a transfer-type decorative sheet, an uncured curable resin layer is provided between the peelable film and the decorative layer, and the curable resin layer is cured by heat during thermoforming and adhered to the adherend. Thereafter, a transfer type decorative sheet having a curable resin layer that peels off the peelable film is known (see, for example, Patent Documents 1, 2, and 3). Since the decorated part of the obtained molded body is covered with the cured resin layer, the decorated part is protected, and a decorated molded body excellent in strength and aesthetic maintenance can be obtained.

However, the transfer type decorative sheet having such a curable resin layer is peeled off from the peelable film when the curable resin is formed on the peelable film, or peeled off after thermoforming. There is a problem that the adhesive film does not peel off well or peels off during thermoforming.
In the transfer type decorative sheet, the peelable film has an adhesive force that does not peel at the time of sheet production or thermoforming, and is required to be peeled off rapidly after thermoforming.
On the other hand, the curable resin layer is uncured or semi-cured during sheet molding. Usually, a curable resin that is substantially non-flowable and non-adhesive at room temperature as described in Patent Document 1 is used because of its ease of handling in a sheet state. The surface state and the surface state after curing are clearly different. That is, it is presumed that the uncured and uncured surface state of the curable resin is compatible with the surface state of the peelable film to be used, but the present knowledge is not clear and is used. The actual situation is that it is selected each time depending on the type of curable resin or the type of peelable film to be used.

JP-A-10-258599 JP-A-10-297185 Japanese Patent Laid-Open No. 2006-212822

  The problem to be solved by the present invention is to have a curable resin layer so that the peelable film does not peel off during sheet molding or during thermoforming, and can be peeled off quickly after thermoforming. It is to provide a transfer type laminated sheet for thermoforming.

The present inventors pay attention to the wetting index as an index for grasping the surface state of the peelable film and the curable resin layer, and the wetting index between the peelable film and the curable resin layer is within a certain range. By using a transfer-type laminated sheet for thermoforming, the above problems have been solved.
It has become clear from experimental values that the wetting index of the curable resin layer is constant from after coating and drying to after thermoforming. Therefore, in the present invention, the wetting index after thermoforming was used as an index.

  That is, the present invention is a laminated sheet for thermoforming in which at least a peelable film layer, a curable resin layer, a decorative layer, and an adhesive layer showing adhesion to an adherend are laminated in this order. Thus, there is provided a laminated sheet for thermoforming in which the absolute value of the difference in wetting index after thermoforming of the peelable film layer and the curable resin layer is in the range of 0 to 12 dyn / cm.

The laminated sheet for thermoforming according to the present invention is a beautiful molded body in which the peelable film is not peeled off during thermoforming and can be peeled off rapidly after thermoforming, so that the decorative part after molding is not damaged. Can be obtained. Moreover, since a decorating part is covered with curable resin, a decorating part is protected and it can obtain the decorating molded object excellent in intensity | strength and aesthetic maintenance.
The laminated sheet for thermoforming of the present invention has sufficient three-dimensional followability and surface protection while maintaining the optimum peeling force of the release sheet before and after molding.

(Peelable film)
The peelable film used in the present invention is preferably a film of a material that can be heat-shaped for thermoforming. Specifically, a material having a storage elastic modulus at a molding temperature of 0.1 MPa to 500 MPa is preferable, and 5 MPa to 100 MPa is more preferable. The preferable molding temperature in the present invention will be described in detail later, but is generally 100 to 170 ° C. in vacuum molding and vacuum / pressure forming, and 70 to 200 ° C. in hot press molding.
The material of the film is specifically a thermoplastic resin such as polyester, such as polypropylene, polyethylene, polyethylene terephthalate, polymethyl methacrylate, polyvinylidene fluoride, polyvinyl chloride, polyvinyl acetal, polycarbonate, polyurethane, and the like. A stretched or unstretched film of a plastic resin, or a film in which the films are multilayered by coextrusion or lamination can also be used. This makes it possible to achieve both surface peelability and moldability. Moreover, a laminated body with resin which improves peelability, such as a silicone resin, a fluorine resin, and amino alkyd, can be used.
Moreover, the method of processing the surface of a peelable film to an appropriate peeling force by the surface treatment method which improves the wettability of film surfaces, such as a corona treatment, can also be used. By this, in the case of a film and a curable resin having a peel strength that is too small, it is possible to adjust the peel strength to be preferable only after molding by adjusting the corona treatment amount.
The thickness of the peelable film is not particularly limited, but is preferably 20 to 400 μm and more preferably 50 to 200 μm because of excellent thermoformability or peelability.
In particular, an unstretched polypropylene film or a biaxially stretched polyethylene terephthalate (PET) film is preferable as a film that does not break during thermoforming and exhibits good peelability after molding. These preferable film thicknesses are 25-200 micrometers, and it is preferable to select optimal film thickness with shaping | molding methods, such as hot press molding and vacuum pressure forming.

  Usually, when manufacturing the lamination sheet for thermoforming of this invention, the organic solvent solution of the below-mentioned curable resin is applied on the said peelable film. Therefore, the material or surface of the peelable film is preferably a film having resistance to the organic solvent used in the organic solvent solution of the curable resin. If a peelable film having low solvent resistance is used, it may be difficult to peel off after molding, or the film may be cracked during thermoforming.

In the present invention, the wetting index of the peelable film layer refers to the wetting index of the surface of the peelable film layer in contact with the curable resin layer. The wetting index is a value measured with a wettability standard indicator according to JIS-K6768.
For the peelable film, the wet index of the curable resin layer described later is measured in advance, and the peelable film is selected such that the absolute value of the difference from the wet index is in the range of 0 to 12 dyn / cm. preferable. For example, when the measured value of the wetting index of the curable resin layer described later is 35 dyn / cm, a polypropylene or polyethylene film having a wetting index of 25 to 45 dyn / cm as the peelable film (wetting index is 25 dyn / cm to 40 dyn / cm), a stretched polyethylene terephthalate film (wetting index is 40 to 50 dyn / cm) is not easily peeled off during coating or drying, and can be peeled off with an appropriate peeling force after molding.

In addition, in the process before and after thermoforming, the peeling force that the curable resin layer described later does not carelessly peel from the peelable film is 0.1 N / cm or more, and more preferably 0.5 N / cm or more. If the peeling force is less than 0.1 N / cm, the cured resin layer may not follow the wrinkles at the time of winding or unwinding the film, and peeling may occur.
On the other hand, the peel force capable of easily peeling the peelable film from the curable resin layer described later after thermoforming is 10 N / cm or less, preferably 5 N / cm or less.

(Curable resin layer)
In the present invention, the curable resin layer is a layer that becomes the outermost surface of the decorated part of the adherend after thermoforming, and has the purpose of protecting the decorated part, maintaining strength, or maintaining aesthetics, and thermoforming. It is a layer excellent in scratch resistance and solvent resistance by being cured using the heat of time. Since it is the objective of protecting a decoration part, it is preferable that it is a transparent or semi-transparent layer. Moreover, in order to maintain the peelability after shaping | molding, the absolute value of the difference of the wetting index before the thermoforming of the said peelable film layer and the said curable resin layer is the range of 0-12 dyn / cm.
The resin composition constituting the curable resin layer is preferably a composition that can be applied to the peelable film layer, and if it is a resin composition that can be cured by heat and / or ionizing radiation, there is no particular limitation. Absent. Specific examples of the resin composition include a resin composition capable of urethane reaction between a hydroxy group and an isocyanate group, a resin composition capable of radical polymerization reaction such as a (meth) acryloyl group and an unsaturated polyester, and a glycidyl group. Examples thereof include a resin composition capable of ring-opening polymerization.

Among them, since the resin has both thermoformability and strength after curing, the resin used is made by pendating the reactive functional group on a thermoplastic resin having a glass transition temperature (hereinafter abbreviated as Tg) of 30 to 100 ° C. Reactive resins are preferred. When Tg is within this range, it is possible to balance printability, moldability and physical properties of the coating film. When Tg is less than 30 ° C., the curable resin layer is likely to be attacked by a solvent when a printed layer or an adhesive layer is formed, and it may be difficult to form a film.
In the present invention, the curable resin layer is preferably semi-cured in advance. The degree of semi-curing is not particularly limited, but when the reaction rate of the functional group contained in the curable resin layer is in the range of 20 to 95%, molding with a high degree of stretching becomes possible at the time of thermoforming in the next step. In addition, it is preferable that the crosslinking reaction can be almost completed only by heat during the molding process. The semi-curing is preferably performed using heat at the time of aging.

Examples of the resin composition capable of undergoing urethane reaction between the hydroxy group and the isocyanate group include an acrylic urethane resin composition containing an acrylic polyol and a polyisocyanate compound.
The acrylic polyol is obtained by homopolymerizing or copolymerizing a vinyl monomer having a hydroxy group by a known method. The hydroxyl value of the acrylic polyol used is preferably in the range of 30 to 120 KOH mg / g, and most preferably in the range of 40 to 100 KOH mg / g.
In the case of semi-curing, the isocyanate reaction rate is preferably 20 to 95%, more preferably 60 to 90%. In particular, when an acrylic polyol obtained by copolymerizing a vinyl monomer having a secondary hydroxy group is used, the degree of semi-curing can be reduced to 20 to 95% by the heat of aging.
Specifically, the acrylic polyol obtained by copolymerizing a vinyl monomer having a primary hydroxy group preferably has a reaction rate of 20 to 80%, and the vinyl monomer having a secondary hydroxy group. The acrylic polyol obtained by copolymerizing is preferably 20 to 95% reaction rate.

  The weight average molecular weight (hereinafter abbreviated as Mw) evaluated by the gel permeation chromatography method (polystyrene standard conversion value) of the acrylic polyol is preferably in the range of 10,000 to 100,000. When the Mw is 10,000 or more, the solvent resistance of the cured coating film tends to be good, and when the Mw is 100,000 or less, the three-dimensional formability tends to be good. A more preferable range is 20,000 to 50,000.

(Polyisocyanate compound)
The polyisocyanate compound used in the present invention is a compound having an average of two or more isocyanate groups in one molecule. Mw is preferably 10,000 or less, more preferably 5,000 or less, and particularly preferably 2,000 or less. Among them, it is preferable to use a trivalent or higher isocyanate compound containing 3 or more isocyanate groups in one molecule.

  Specific examples of the trivalent or higher isocyanate compound include 2-isocyanatoethyl-2,6-diisocyanatocaproate, 1,3,5-triisocyanatocyclohexane, 2,4,6-triisocyanate. Aliphatic triisocyanates such as cycloheptane, 1,2,5-triisocyanatocyclooctane, aromatic triisocyanates such as 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatonaphthalene, diisocyanates And polyisocyanates having a so-called isocyanurate ring structure obtained by cyclization and trimerization.

  The blending ratio of the acrylic polyol and the polyisocyanate compound is preferably in the range of 0.5 to 1.5 equivalents of isocyanate groups in the polyisocyanate compound per equivalent of hydroxyl groups in the curable resin layer, particularly 0.7 to A range of 1.2 equivalents is preferable from the balance of various performances of the cured coating film.

(Curing catalyst)
When the acrylic polyol and the polyisocyanate compound are reaction-cured, a known curing catalyst can be added as necessary.
Specifically, for example, N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 ( DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), amine compounds such as tri-n-butylamine,

  Various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxylpropyl) ammonium salt and the like, chloride, bromide, carboxylate, hydroxide, etc. as typical counter anions There are various organic metal compounds such as quaternary ammonium salts, dibutyltin dilaurate, dibutyltin acetate, lead dioctylate, cobalt naphthenate and the like.

  The addition amount of the curing catalyst is not particularly limited, but if it is added excessively, the pot life (pot life) may be shortened and the composition containing acrylic polyol and polyisocyanate compound may be gelled. Usually, it is preferable to add 0.01 to 1 part by weight of the curing catalyst with respect to 1000 parts by weight of the composition.

The curable resin layer is preferably semi-cured before thermoforming in an isocyanate reaction rate of 20 to 95%. Depending on conditions such as heating during molding, the curing reaction is insufficient when the reaction rate is less than 20%, so the solvent of the coating solution is cured during subsequent printing of the decorative layer, coating, and application of the adhesive layer. It may penetrate into the resin layer, making it difficult to dry the solvent or causing the protective film to float or wrinkle. On the other hand, if the reaction rate exceeds 95%, the curable resin layer may be cracked or peeled by stretching during thermoforming.
The reaction rate is more preferably 60 to 95%.

  The reaction rate mentioned here is a test film obtained by applying a curable composition of a curable resin layer using an appropriate transparent resin film, for example, a 25 μm PET film, and curing it in the same manner as actual drying and curing conditions. And two types of correction films that were completely cured (heat treatment at 110 ° C. for 2 hours), and cured isocyanate functional groups by transmission method or ATR method using FT-IR (Fourier transform infrared spectrophotometer) It is a value obtained by measuring the absorbance peak heights of the IR spectra before and after and calculating from the following formula.

  Examples of the resin composition capable of radical polymerization reaction such as the (meth) acryloyl group and unsaturated polyester include, for example, vinyl monomers having a reactive group such as hydroxy (meth) acrylate and glycidyl (meth) acrylate. The copolymer is reacted with a monomer having a group capable of reacting with the reactive group of the copolymer, such as (meth) acrylic acid or an isocyanate group-containing (meth) acrylate, and having a radical polymerizable group. The (meth) acrylic resin (a) having a radically polymerizable group in the side chain, and the epoxy acrylate having a (meth) acrylic group obtained by reacting the end of the epoxy resin with (meth) acrylic acid, etc. (B) Unsaturated polyester (c) etc. which condensed carboxylic acid which has unsaturated groups, such as fumaric acid, with diol can be used.

The Mw of the (meth) acrylic resin (a) having a radical polymerizable group in the side chain is from 50,000 to 500,000, preferably from 100,000 to 300,000. When Mw exceeds 500,000, the viscosity of the coating composition tends to increase, and gelation may occur or coating properties may be deteriorated.
Tg is preferably 40 ° C to 120 ° C, more preferably 50 to 110 ° C. When the Tg is less than 40 ° C., the adhesiveness of the resin itself is increased, and the handleability tends to be lowered, such as difficulty in winding during film production. On the other hand, when the glass transition temperature exceeds 120 ° C., the flexibility of the resin is lowered, so that it may be easily peeled off from the peelable film during handling of the film, or the curable resin layer after coating may be cracked. is there.

The epoxy acrylate (b) is (meth) acrylate obtained by reacting polyepoxide with (meth) acrylic acid or its anhydride. The epoxy acrylate used in the present invention preferably has an average number of functional groups of 1.5 or more on average. If the average number of functional groups is less than 1.5 on average, the crosslinking density when cured is small, and the resulting coating film may have poor adhesion performance. More preferably, the average number of functional groups is 2 to 5.
Specific examples of the polyepoxide include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and the like, and hydrogenated aromatic rings of bisphenol type epoxy resin. Among them, bisphenol type epoxy resin is preferable because it can form a cured coating film having an excellent balance between hardness and elongation, and bisphenol A type epoxy resin is most preferable.
These polyepoxides can be used alone or in combination of two or more.
As the epoxy acrylate (b), those having a Mw of 1000 to 3000 are particularly preferred because of their low fluidity after coating and drying, and excellent stability after winding of the coating film.

  Examples of the carboxylic acid having an unsaturated group that is a raw material of the unsaturated polyester (c) include maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, and the like. Two or more of these may be used in combination. Other polybasic acids used as needed include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, succinic acid, azelaic acid, adibic acid, tetrahydrophthalic acid, tetrahydro Phthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, endomethenetetrahydrophthalic anhydride, anthracene-maleic anhydride adduct, rosin-maleic anhydride adduct, het acid, het anhydride, tetrachlorophthalic acid, tetrachloro Chlorinated polybasic acids such as phthalic anhydride, and halogenated polybasic acids such as tetrabromophthalic acid and tetrabromophthalic anhydride are used. Two or more of these may be used in combination.

Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 4-butanediol, 2,3-butanediol, 1,5-pentanediol, and 1,6-hexane. Examples include diol, triethylene glycol, neopentyl glycol and the like.
The reaction between the carboxylic acid having an unsaturated group and the diol may be performed by a known polycondensation reaction.
Examples of the organic peroxide used for curing include curing catalysts such as methyl ethyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide, and lauroyl peroxide. This organic peroxide is normally mix | blended in the ratio of 0.5 to 3.0 weight% with respect to an unsaturated polyester resin composition.

The wetting index of the curable resin layer is a value measured with a wettability standard indicator or the like according to JIS-K6768, similarly to the measurement of the wetting index of the peelable film layer described above. In the curable resin layer, it refers to the wetting index of the surface in contact with the peelable film layer.
As described above, it has become clear from experimental values that the wetting index of the curable resin layer is substantially constant from after coating and drying to after thermoforming. As an example, the wetting index at each time of the production process when a curable resin layer is formed using an acrylic urethane resin composition is shown.

A coating solution in which an acrylic polyol having a hydroxyl value of 40 (KOHmg / g) and an approximately equivalent amount of polyfunctional isocyanate are mixed is applied to a peelable film (step 1) and then dried at 80 ° C. for 2 minutes (step 2). Next, gravure printing was performed using gravure ink (step 3), and then dried at 70 ° C. for 1 minute (step 4). After the adhesive solution is applied (Step 5), it is dried at 80 ° C. for 2 minutes (Step 6), and after aging at 60 ° C. for 3 days (Step 7), press molding is performed at 140 ° C. (Step 8). Table 1 shows the wetting index in each of the steps 1 to 8. This shows that there is no correlation between the reaction rate of the isocyanate and the wetting index, and the wetting index does not change in each step. Therefore, it can be determined that the wetting index is influenced by the skeletal structure such as acrylic polyol regardless of the reaction rate of the reactive group such as isocyanate.
Therefore, in the present invention, the wetting index after thermoforming is measured and used as the wetting index of the curable resin layer.

In the present invention, the absolute value of the difference between the wetting index of the peelable film layer and the wetting index after thermoforming of the curable resin layer is in the range of 0 to 12 dyn / cm.
When the difference in wetness index is within this range, the peelable film does not peel off during thermoforming, and can be peeled off quickly after thermoforming, and a beautiful molded body is obtained without damaging the decorative part. be able to.
When the wetting index of the curable resin layer is 34 to 42 dyn / cm, the range of selection of the peelable film that can be used is widened. The wetting index can be adjusted by appropriately selecting the resin skeleton as described above.

Moreover, when manufacturing the thermoformed laminated sheet of this invention as mentioned above, the said curable resin layer is coated on the said peelable film as an organic solvent solution. Therefore, the organic solvent to be used is preferably a solvent that does not attack the material or surface of the peelable film as much as possible.
Specifically, it has compatibility with the peelable film to be used, but in the case of a film having excellent solvent resistance such as polyolefin film such as polyethylene and polypropylene and biaxially stretched polyethylene terephthalate, an ester solvent such as ethyl acetate, A ketone solvent such as methyl ethyl ketone and an aromatic solvent such as toluene and xylene are preferably used. In the case of an unstretched polyester film, a solvent whose solubility is slightly lowered with alcohols such as n-butanol and i-propyl alcohol is preferable.

  Although the film thickness of the said curable resin layer does not have a restriction | limiting in particular, The range of 2-50 micrometers is preferable, More preferably, it is 5-30 micrometers. When the film thickness is less than 2 μm, the scratch resistance and solvent resistance decrease, and when the film thickness exceeds 50 μm, the stretchability during molding tends to decrease.

(Decoration layer)
The printing ink or paint used for forming the decorative layer in the present invention is a printing ink or paint that can be printed or applied to the surface of the curable resin layer or a support film described later, and is fading or discoloring during thermoforming. It is preferable that sufficient flexibility is obtained when the transfer layer is transferred to the transfer target. A colored layer having no pattern can also be formed by coating.

Although there is no restriction | limiting in particular in the ink to be used, It is preferable to use the colorant which does not have a fear of fading at the time of thermoforming. As the colorant contained in the ink, a pigment is preferable, and any of an inorganic pigment and an organic pigment can be used.
For example, general-purpose coloring pigments include carbon black as a black pigment; yellow lead, yellow lead, anthraquinone yellow, mineral fast yellow, titanium yellow; red pigments such as Bengala, cadmium red, quinacridone red, permanent red 4R, and risol red. , Pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake; blue pigment, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue; Chrome green, chromium oxide, pigment green B, malachite green lake; examples of white pigments include titanium white. Examples of pigments that exhibit a metallic tone include metal powder pigments (aluminum, bronze, etc.), metal foil pigments (aluminum, bronze, etc.), metal vapor-deposited foil pigments (pulverized films of plastics, etc., on which aluminum, bronze, etc. are deposited). It is done. Pearl pigments (such as those obtained by pulverizing natural pearls, flaky materials such as mica, aluminum, glass, etc., coated with titanium oxide, iron oxide, etc.) as pigments that exhibit pearl tone, multicolor effect, polarization effect, hologram, etc. Etc. Inorganic extender pigments such as lime carbonate powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, abrasive powder, Silicone, glass beads and the like can also be used.
The varnish resin contained in the ink is, for example, an acrylic resin system, a polyurethane resin system, a polyester resin system, a vinyl resin system (vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), a chlorinated olefin resin system, Known inks such as ethylene-acrylic resin, petroleum resin, and cellulose derivative resin can be used. Among these, polyurethane resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, cellulose derivative resin systems are preferably used because they are excellent in solubility in organic solvents, fluidity, pigment dispersibility, and transferability. Polyester resin system and cellulose derivative resin system are preferable, and polyurethane resin system and cellulose derivative resin system are particularly preferable.

As a method for forming the decoration layer, gravure printing, offset printing, screen printing, ink jet printing, thermal transfer printing, or the like can be used. Gravure printing is particularly preferred from the viewpoint of flexibility. The coating methods corresponding to these printing methods are coating methods such as roll coating, comma coating, rod gravure coating, micro gravure coating, gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, Coating methods such as an air knife coater, kiss touch coater, kiss touch reverse coater, comma coater, comma reverse coater, and micro gravure coater can be used. In the case of ink, the entire surface (100% in the case of halftone dots) may be printed or coated with the same ink, or partially printed so as to form a pattern.
It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-7 micrometers.

  Unless detrimental to design and spreadability, antifoaming agent, anti-settling agent, pigment dispersant, fluidity modifier, anti-blocking agent, antistatic agent, antioxidant in curable resin layer and decorative layer Various conventional additives such as a light stabilizer and an ultraviolet absorber may be added.

(Adhesive layer)
Examples of the adhesive that can be used for the adhesive layer in the present invention include a phenol resin adhesive, a resorcinol resin adhesive, a phenol-resorcinol resin adhesive, an epoxy resin adhesive, a urea resin adhesive, and a polyurethane adhesive. Thermosetting resin adhesives such as polyaromatic adhesives, radical reaction type adhesives composed of radically polymerizable compositions such as unsaturated polyesters and acrylates, vinyl acetate resins, acrylic resins, acrylic urethane resins, ethylene Thermoplastic resin adhesives such as vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, nylon and cyanoacrylate resin, chloroprene adhesives, nitrile rubber adhesives, SBR adhesives, natural rubber adhesives, etc. Examples thereof include rubber adhesives.
As the adhesive, acrylic, rubber, polyalkyl silicon, urethane, polyester, etc. are preferably used.

The adhesive is preferably selected as appropriate according to the adherend to be used. For example, when the adherend is a resin molded body, an adhesive of an acrylic resin or a polypropylene-based resin is preferable, and an adhesive of an acrylic urethane resin is preferable because the followability of elongation during vacuum molding is good. In addition, when a sheet molding compound (SMC) or a bulk molding compound (BMC), which will be described later, is used as an adherend and is hot-pressed in a press mold, the adherend undergoes radical polymerization during decorative molding. Therefore, an adhesive made of a radical polymerizable thermosetting resin composition is preferable. Examples of the adhesive made of a radical polymerizable thermosetting resin composition include (meth) acrylic resin (a), epoxy acrylate (b), and unsaturated polyester (c) used in the above-described curable resin layer. For example, an adhesive having a thermal polymerization initiator added thereto can be used.
These can be used alone or in combination. These adhesives may or may not be tacky after coating, but they need to be viscous so that they do not flow during winding or hot pressing, and are therefore preferably slightly crosslinked during film lamination.

In the present invention, a gravure coater, a gravure reverse coater, a flexo coater, a blanket coater, a roll coater, a knife coater, an air knife coater, a kiss touch coater, a comma coater, or the like can be used for coating the adhesive. The coating amount is preferably in the range of 0.1 to 30 g / m ² , particularly preferably ² to 10 g / m ² . When the amount is less than 2 g / m ² , the adhesive strength is weakened. When the amount is more than 10 g / m ² , the drying property is lowered and the appearance tends to be poor. The thickness of the adhesive layer is preferably in the range of 0.1 to 30 μm, more preferably 1 to 20 μm, and particularly preferably 2 to 10 μm.

(Film production method)
The laminated sheet for thermoforming of the present invention is obtained by forming a curable resin layer on a peelable film and sequentially laminating a decorative layer and an adhesive layer on the layer.
As a method for forming a curable resin layer on a peelable film, for example, a gravure coater, a gravure reverse coater, a flexo coater, a blanket coater, a roll coater, a knife coater, an air knife coater, a kiss touch coater, a comma coater, a reverse coater, A coating method such as spray coating, or a printing method such as gravure printing, offset printing, screen printing, ink jet printing, or thermal transfer printing can be used.

The decoration layer may be printed directly on the curable resin layer by gravure printing or screen printing, or printed on a support film having a peelability made of a material such as polypropylene, polyethylene, polyester, nylon, or release-treated polyethylene terephthalate. The printed decorative layer surface and the surface of the curable resin layer are made to face each other and bonded together by dry lamination (dry lamination method), the support film is peeled off, and the decorative layer is transferred onto the curable resin layer. May be. Depending on the composition of the curable resin layer, the organic solvent contained in the printing ink may dissolve the curable resin layer that becomes the printing surface during printing, so the latter dry lamination method is preferable.
In the method of transferring the decorative layer to the curable resin layer by the dry lamination method, the uncured or semi-cured curable resin layer exhibits adhesiveness at the laminating temperature, and an adhesive force with the opposing decorative layer is generated. The lamination temperature at this time is preferably 60 to 100 ° C., although it depends on the Tg and the degree of cure of the curable resin layer.

(Adherent)
The adherend that can be used in the present invention is not particularly limited. For example, in the three-dimensional vacuum molding overlay (TOM) method, a plastic lithographic plate or a three-dimensional molded body can be used. In the insert injection molded body, a molten resin is injected to obtain a molded body in a state where the pre-molded laminated sheet for thermoforming of the present invention is attached in a mold. The material of the adherend of such vacuum forming overlay or insert injection molding is not particularly limited, but generally, ABS resin, AS resin, polypropylene resin, polystyrene resin, polyethylene resin or the like is used.

In the press molding method, a steel plate, an aluminum plate, a metal plate such as a magnesium plate, a fiber reinforced thermoplastic resin composite material (FRTP) or a fiber reinforced thermosetting resin composite material (FRP) can be used. Examples of the FRP include sheet molding compound (SMC) in which a reinforcing agent is impregnated with a mixture of resin and filler, and bulk molding compound (BMC) in which SMC material is kneaded. Examples of thermosetting resins used for these include unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, thermosetting acrylic resins, melamine resins, guanamine resins, phenol resins, epoxy resins, and two-component curable polyurethanes. Examples thereof include resins. Examples of other materials include reinforcing agents such as fiber trapping agents such as glass fibers, carbon fibers, asbestos, and potassium titanate, catalysts, fillers, release agents, and the like. The content of the reinforcing agent is usually 10 to 70% by weight. As the filler, powders of calcium carbonate, barium sulfate, aluminum hydroxide and the like are used. As the mold release agent, zinc stearate or the like is used. In addition, reaction diluents such as styrene monomer and polyfunctional acrylate (or methacrylate) monomer, cross-linking agents such as isocyanate and amine, benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl perpenzoate, organic as required A polymerization initiator such as a sulfonate (curing catalyst), a curing accelerating catalyst such as cobalt naphthenate and manganese naphthenate, a coloring agent such as titanium dioxide, carbon black, and a petal are added for use. These materials are desirably selected as appropriate in consideration of the application and compatibility with the adhesive.
FRP is a thermosetting resin that is cured by heat at the time of thermoforming to form a molded body. When the laminated sheet for thermoforming of the present invention is sandwiched and molded, thermosetting is used as an adhesive for the laminated sheet. When an adhesive having a reaction system similar to that of a resin is used, a molded body having better adhesiveness can be obtained.

(Molding method)
The laminated sheet for thermoforming according to the present invention is a vacuum forming method in which the decorative film having a decorative layer is sufficiently thermoplasticized and then shaped into a vacuum state, a vacuum / pressure forming method, or a vacuum for the sheet in advance. Film insert injection molding method, three-dimensional overlay vacuum molding method, concave mold, which is molded by injecting molten resin after temporary molding by molding method, press molding method, etc. It can be used as a transfer decorative sheet such as a press molding method (match mold molding method) in which the sheet and the adherend are sandwiched between a convex mold and a convex mold.

(Vacuum forming method, vacuum pressure forming method)
There are no particular limitations on the vacuum pressure forming method or the forming conditions of the vacuum forming. For example, using a far-infrared heater, the heater temperature is 200 to 500 ° C., the indirect heating time is 5 to 30 seconds, and the temperature at which the sheet can be formed, for example, dynamic viscoelasticity measurement obtained by the JIS K7244-1 method ( Hereinafter, it is molded in a state where the storage elastic modulus (E ′) of DMA is set to a temperature of 1 to 250 MPa under measurement conditions of a frequency of 1 Hz and a heating rate of 3 ° C./min.

(Film insert injection molding method)
In addition, after the thermoforming laminate sheet of the present invention is formed by the vacuum forming method or the like, the thermoforming laminate sheet is injected or molded so that the thermoplastic resin film layer and the concave mold of the injection mold are opposed to or in contact with each other. Inserted into a mold, or the laminated sheet for thermoforming of the present invention is subjected to a vacuum forming method (including a plug assist vacuum forming method), a vacuum / pressure forming method (including a plug assist vacuum / pressure forming method), a hot plate / pressure forming method. Then, after forming a three-dimensional shaped molded body using a press molding method or the like, it is inserted so as to be in contact with the concave mold of the injection molding die, clamped, and filled with an injection resin from the back side of the molded body, An injection molded body can also be obtained.

(Three-dimensional vacuum forming overlay method)
In addition, the three-dimensional vacuum forming overlay method is a method in which the thermoformed laminated sheet of the present invention is directly heat-formed on an adherend that is a three-dimensionally formed body without using a mold. Specifically, an adherend that is a three-dimensional molded body is placed in a vacuum coating molding machine, and waits in a non-heated zone of two vacuum zones partitioned by the thermoforming laminated sheet of the present invention. After being sufficiently heated and softened in a vacuum, the adherend protrudes onto the sheet, and the sheet is three-dimensionally shaped on the adherend. At the same time, since compressed air is introduced to the heating zone, the coated sheet can be closely attached to the adherend in detail. There are no particular limitations on the molding conditions, but in general, the storage elastic modulus (E ′) of dynamic viscoelasticity measurement (hereinafter referred to as “DMA”) determined by the JIS K7244-1 method has a frequency of 1 Hz and a heating rate of 3 It shape | molds in the state made into the temperature used as 1-700 Mpa on the measurement conditions of C / min.

(Hot press molding method)
In the hot press molding method, the laminated sheet for thermoforming of the present invention is overlaid on the aforementioned SMC or BMC and inserted into a molding die, the die is closed and heated under pressure, and an uncured resin is polymerized and cured. This is a method for obtaining a decorated solid molded product. Although there are no particular limitations on the molding conditions, generally, the pressure is about 2 to 20 MPa at about 120 to 150 ° C., and the molding time is 4 to 20 minutes.
Normally, at the time of molding, the lower mold is filled with SMC or BMC, placed on the filled SMC or BMC with the decorative film adhesive layer on the bottom, and the upper mold is closed and heated and heated for a predetermined time. Apply pressure. At this time, in order to remove air between the film and the filling, a decompression process may be performed.

  The peelable film is peeled off from the molded body after the molding to obtain a decorated molded body. The peeling method is not particularly limited. For example, the boundary end face may be lifted and peeled off. When it is difficult to lift the boundary end face, an adhesive tape or the like may be attached to make a peeling end and then peeled off.

  Hereinafter, the present invention will be described with specific examples, but the present invention is not limited thereto. In addition, the physical-property evaluation in an Example and a comparative example was performed with the following measuring method or test method. In the examples, “part” and “%” are both based on mass.

(Measurement method of wetting index of peelable film and curable resin layer)
According to JIS-K6768, Wako Pure Chemical's wettability standard indicator of 22.7 dyn / cm to 70 dyn / cm is prepared in various ways, and the indicator is applied to the film surface with a cotton swab. The indicator was the wetting index of the film or curable resin.

(Peelability evaluation of peelable film layer after molding decoration)
The peelable film was coated with a curable resin, a decorative layer, and an adhesive layer, laminated in order, and wound up, and it was confirmed whether there was any peeling between the peelable film and the curable resin layer. Those with peeling were marked with ×, and those without peeling were marked with ○. Next, Nichiban cellophane tape (Nichiban is a registered trademark) was attached to the adhesive layer, and the cellophane tape was peeled off. Further, after thermoforming, the case where the peelable film was peeled off from the adherend was evaluated as “◯”, the case where the peelable film could not be peeled off, the decorative part was partially damaged, or the peelable film was broken.

(Adhesion measurement method for the adherend of the decorative part after molding decoration)
The adhesion of the decorative part after molding decoration to the adherend was evaluated based on a cross-cut tape method (JIS K5400) with a maximum of 10 points.

(Adhesion measurement method after hot water treatment for adherend of decorated part after molding decoration)
The molded body after molding decoration is heated and held in hot water (water temperature 98 ° C.) for 30 minutes, and then, according to the cross-cut tape method (JIS K5400), the cross section of 1 × 1 mm with a cutter is added to the decorative section 100 After making an individual and sticking an adhesive tape on the part, this adhesive tape was peeled off rapidly, the peeling state of the coating film was observed visually, and the ink adhesiveness was evaluated with a maximum of 10 points.

(Method for producing thermoformed laminated sheet)
(Peelable film)
As the peelable film, (A-1) to (A-5) were used.
Peelable film (A-1): Teijin Teflex FT-7 (biaxially stretched polyethylene terephthalate film, wetting index 42 dyn / cm, film thickness 50 μm)
Peelable film (A-2): Pyrene P1011 manufactured by Toyobo (unstretched polypropylene film, wetting index 28 dyn / cm, film thickness 50 μm),
Peelable film (A-3): Pyrene P2002 manufactured by Toyobo (biaxially stretched polypropylene film, wetting index 30 dyn / cm, film thickness 50 μm),
Release film (A-4): Soft Shine resin coated surface manufactured by Toyobo (biaxially stretched polyethylene terephthalate film, wetting index 65 dyn / cm)
Release film (A-5): Unitika SC50 (silicon release film wettability index 22.7 dyn / cm)

(Composition for curable resin layer)
(Composition for curable resin layer (B-1))
In a 2 L reaction vessel equipped with a temperature controller, a nitrogen introduction tube, and a stirrer, 282 parts of ethyl acetate was charged, and the temperature was raised to 75 ° C. after nitrogen substitution. Separately, 300 parts of methyl methacrylate, 100 parts of n-butyl methacrylate, 60 parts of 2-hydroxypropyl methacrylate (100 mol% of secondary hydroxyl group), 4 parts of n-butyl acrylate, and 2 parts of styrene monomer were mixed well. Solution (hereinafter referred to as monomer solution), 50 parts of ethyl acetate, 2.5 parts of perbutyl O (trade name, manufactured by NOF Corporation), 2 parts of ABN-V (trade name, manufactured by Nippon Hydrazine Industry Co., Ltd.), ABN- A solution (hereinafter referred to as a catalyst solution) in which 2.5 parts of E (trade name, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) was mixed well was charged into a dropping device, and immediately purged with nitrogen.
The monomer solution and the catalyst solution were respectively added dropwise to the reaction vessel over 4 hours in a nitrogen atmosphere. During the charging, the dropping rate of the monomer solution and the catalyst solution was adjusted so that there was no sudden rise in reaction temperature. After completion of dropping, 166 parts of ethyl acetate was charged to obtain an acrylic polyol (B-1) having a nonvolatile content of 50%. The acrylic polyol (B-1) had an Mw of 30,500, a hydroxyl value of 40, an acid value of 0.1 or less, and a calculated Tg of 69 ° C.

  In 50 parts of the acrylic polyol (B-1), Bernock DN-981 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., isocyanurate ring-containing polyisocyanate, Mw1000, non-volatile content 75% (solvent: ethyl acetate) ), 6.8 parts of isocyanate (NCO) functional group concentration 13.7%), 0.25 part of 1% dibutyltin dilaurate butyl acetate solution) as a curing catalyst, and 64 parts of ethyl acetate as a diluting solvent. Composition (1) for the conductive resin layer was prepared. The NCO / OH equivalent ratio, that is, the equivalent ratio of the isocyanate group amount of the curing agent to the acrylic polyol (B-1) is 1.0.

(Composition for curable resin layer (B-2))
In the same manner as for the curable resin layer composition (B-1), 100 parts of methyl methacrylate, 100 parts of n-butyl methacrylate, 100 parts of 2-hydroxyethyl methacrylate, 4 parts of n-butyl acrylate, styrene monomer Two parts were polymerized to obtain an acrylic polyol (B-2) having a nonvolatile content of 50%. Mw of acrylic polyol (B-2) was 35,500, and the hydroxyl value was 139.
20 parts of an isocyanate-containing methacrylate (product name: Karenz MOI) made by Showa Denko is dropped on the acrylic polyol (B-2), reacted at 60 ° C. for 1 hour, and a composition for a curable resin layer having a methacryloyl group in the side chain. A product (B-2) was obtained.

(Decoration layer)
As the decorative layer ink, an ink having the following composition was used.
(Ink composition, black, brown, white)
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (black, brown, white): 10 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts

(Adhesive (D-1))
50 parts of epoxy acrylate resin “Dicklight UE8200” manufactured by Dainippon Ink and Chemicals, 50 parts of polyester “Byron 500” manufactured by Toyobo, 70 parts of ethyl acetate, 30 parts of toluene, 0.1 part of peroxide “Perbutyl O” manufactured by Nippon Oil & Fats And an adhesive (D-1) comprising 0.1 part of “Perhexa A” manufactured by the same company.

(Adhesive (D-2))
Nippon Iupika epoxy acrylate resin "Neopol 8250H" 70 parts, Toyobo polyester "Byron 500" 30 parts, ethyl acetate 70 parts, toluene 30 parts, Nippon Oil & Fats peroxide "Perbutyl O" 0.1 parts, and the company An adhesive (D-2) comprising 0.1 part of “Perhexa A” was prepared.

(Adhesive (D-3))
Two-component polyester urethane adhesive (Adhesive (D-3) obtained by mixing “LX-630PX” manufactured by Dainippon Ink & Chemicals, Inc. and curing agent “KR-90” in a weight ratio of 42: 1. Was prepared.

(Example 1)
(Method for producing laminated sheet for thermoforming)
The curable resin layer (B-1) was coated on the peelable film (A-1) with a rod gravure coater so as to have a dry film thickness of 20 μm, and dried at 80 ° C. for 2 minutes.
Unstretched polypropylene film Pyrene P1011 (Toyobo Co., Ltd., thickness 50 μm) is used as a support film (E-1), and a gravure four-color printing machine is used on the film with a decorative layer ink having a thickness of 3 μm. Was printed to form a printed film. The surfaces of the curable resin layer (B-1) coated on the peelable film (A-1) and the printed layer surface of the printed film were overlapped with each other and laminated with a 90 ° C. heat roll. . The support film (E-1) could be peeled off from the printed layer after lamination, and the printed layer (decorative layer) transferred cleanly to the surface of the curable resin layer.
On the other hand, the adhesive (D-1) was applied to a dry film thickness of 15 μm by using a unitized release polyethylene terephthalate film made of Unitika as a support film (E-2), and then dried at 80 ° C. for 2 minutes. did. The adhesive layer of the adhesive film is opposed to the decorative layer of the sheet formed by coating the peelable film (A-1) / curable resin layer (B-1) / decorative layer in this order. Laminated, laminated at 60 ° C. and wound up. The support film (E-2) could be peeled off from the adhesive layer after lamination, and the adhesive layer transferred cleanly to the decorative layer surface.

(Laminated sheet forming method for thermoforming)
Next, the obtained laminated sheet for thermoforming was placed with the adhesive layer on the lower mold side of the lower mold 140 ° C. and the upper mold 150 ° C. hot press mold, and a 1 mm thick new sheet was formed on the adhesive layer. 600 g of SMC Dick Mat 2400 manufactured by Dick Kako was installed, the upper mold was lowered, and hot pressing was performed at a pressure of 20 MPa for 4 minutes. After pressing, the decoratively molded plate is taken out and the PET film on the surface is peeled off. Then, a sheet portion composed of a curable resin layer (B-1) / decorative layer / adhesive layer (D-1) is added to the surface of the molded body. A decorated molding was obtained.
The evaluation is shown in Table 2.

(Example 2)
The sheet manufacturing method and molding of Example 1 except that the peelable film (A-1), the curable resin layer (B-1), and the adhesive (D-1) used were changed as shown in Table 2. In the same manner as the method, a molded product was obtained in which the surface of the molded body was decorated with a sheet portion composed of a curable resin layer (B-2) / decorative layer / adhesive layer (D-2). The evaluation is shown in Table 2.

(Example 3)
(Method for producing laminated sheet for thermoforming)
The curable resin layer (B-1) was coated on the peelable film (A-3) with a rod gravure coater so as to have a dry film thickness of 20 μm, and dried at 80 ° C. for 2 minutes. On the curable resin layer (B-1), a wood grain pattern was printed directly with a gravure four-color printing machine with a thickness of 3 μm using a decoration layer ink to form a decoration layer.
On the other hand, the adhesive (D-3) was applied to a dry film thickness of 15 μm using a united release film made of united polyethylene terephthalate as a support film (E-2), and then dried at 80 ° C. for 2 minutes. did. The adhesive layer of the adhesive film is opposed to the decorative layer of the sheet formed by coating the peelable film (A-3) / curable resin layer (B-1) / decorative layer in this order. Laminated, laminated at 60 ° C. and wound up. The support film (E-2) could be peeled off from the adhesive layer after lamination, and the adhesive layer transferred cleanly to the decorative layer surface.

(Laminated sheet forming method for thermoforming)
Next, the obtained laminated sheet for thermoforming was placed with the adhesive layer on the lower mold side of the lower mold 80 ° C. and the upper mold 80 ° C. hot press mold, and the plate thickness of 1 mm was formed on the adhesive layer. A steel plate was installed, the upper mold was lowered, and hot pressing was performed at a pressure of 20 MPa for 4 minutes. After pressing, the decoratively molded plate is taken out and the PET film on the surface is peeled off. Then, a sheet portion composed of a curable resin layer (B-1) / printing layer / adhesive layer (D-3) is added to the surface of the molded body. A decorated molding was obtained.
The evaluation is shown in Table 2.

Example 4
Except that the peelable film (A-3), the curable resin layer (B-1), and the adhesive (D-3) used were changed as shown in Table 2, the same as the sheet manufacturing method of Example 3. Thus, a laminated sheet for thermoforming comprising a peelable film layer (A-3) / curable resin layer (B-2) / decorative layer / adhesive layer (D-3) was obtained.
(Sheet forming method)
Next, the laminated sheet for thermoforming and the ABS three-dimensional molded body were attached to an overlay vacuum molding machine (the three-dimensional molded body is an ABS injection molded body). The sheet was heated under reduced pressure to a film surface temperature of 120 ° C., and the molded product was pressed in a molding machine. The laminated sheet for thermoforming closely adhered following the three-dimensional shape of the molded product. Next, when the system is returned to normal pressure, the decorated three-dimensional molded body is taken out and the peelable film (A-2) is peeled off, the decorative layer is not peeled off from the molded product, and the curable resin layer (B- 2) A molded product in which a sheet portion composed of a decorative layer / adhesive layer (D-3) was decorated on the surface of the molded body was obtained.

(Example 5)
Except for changing the peelable film (A-1), the curable resin layer (B-1), and the adhesive (D-1) to be used as described in Table 3, it is the same as the sheet manufacturing method of Example 1. Thus, a laminated sheet for thermoforming comprising a peelable film layer (A-1) / curable resin layer (B-1) / decorative layer / adhesive layer (D-3) was obtained.
The curable resin layer (B-1) / decorative layer / adhesive layer (D-3) was obtained in the same manner as in the sheet molding method of Example 4 except that the obtained laminated sheet for thermoforming was formed at a molding temperature of 170 ° C. ) Was obtained by decorating the surface of the molded body.
The evaluation is shown in Table 2.

(Comparative Example 1)
Except having changed the peelable film (A-3), the curable resin layer (B-1), and the adhesive (D-3) to be used as described in Table 3, it is the same as the sheet manufacturing method of Example 3. Thus, a laminated sheet for thermoforming comprising a peelable film layer (A-4) / curable resin layer (B-2) / decorative layer / adhesive layer (D-1) was obtained.
In the same manner as in the sheet forming method of Example 1, the sheet portion formed of the curable resin layer (B-1) / decorative layer / adhesive layer (D-1) was formed on the surface of the molded body. A molded product decorated in the above manner was obtained. The evaluation is shown in Table 3.
The absolute value of the difference in wetting index between the peelable film (A-4) and the curable resin layer (B-1) is 29, and the peelable film (A-4) is not peeled off. Breaking or peeling occurred from the cured resin layer, and the desired decorative molded body could not be obtained.

(Comparative Example 2)
Except having changed the peelable film (A-3), the curable resin layer (B-1), and the adhesive (D-3) to be used as described in Table 3, it is the same as the sheet manufacturing method of Example 3. Thus, a laminated sheet for thermoforming comprising a peelable film layer (A-2) / curable resin layer (B-1) / decorative layer / adhesive layer (D-3) was obtained.
The obtained laminated sheet for thermoforming was treated in the same manner as the sheet forming method of Example 4, and the sheet portion comprising the curable resin layer (B-1) / decorative layer / adhesive layer (D-3) was the surface of the molded body. A molded product decorated in the above manner was obtained. The evaluation is shown in Table 3.
The absolute value of the difference in wetting index between the peelable film (A-2) and the curable resin layer (B-1) is 15, and the peelable film (A-2) does not peel off. Breaking or peeling occurred from the cured resin layer, and the desired decorative molded body could not be obtained.

(Comparative Example 3)
In the same manner as in Example 1 sheet manufacturing method, when the curable resin layer (B-1) is formed on the peelable film (A-5) and then wound, peeling is observed at the interface between the film and the curable resin layer. It was. The evaluation is shown in Table 3.

Claims (4)

At least a peelable film layer, a curable resin layer, a decorative layer, and a laminated sheet for thermoforming in which an adhesive layer exhibiting adhesiveness to an adherend is laminated in this order, the peelable film A laminated sheet for thermoforming, characterized in that the absolute value of the difference in wetting index between the layer and the curable resin layer after thermoforming is in the range of 0 to 12 dyn / cm. 2. The thermoforming according to claim 1, wherein the curable resin layer contains a thermoplastic resin having a hydroxy group and an isocyanate compound, and the reaction rate of the hydroxy group and the isocyanate group is in the range of 20 to 95%. Laminated sheet. The laminated sheet for thermoforming according to claim 1, wherein the adhesive layer exhibiting adhesiveness to the adherend is a layer made of a radical polymerizable thermosetting resin composition. The laminated sheet for thermoforming according to claim 1, wherein the adherend is a three-dimensional formed body.